Polyazido compounds

ABSTRACT

The compound 2,2-bis(azidomethyl)oxirane, whose structure is depicted below, is disclosed:

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims benefit under 35 USC 119(e) of provisionalapplication 60/319,801, filed Dec. 19, 2002, the entire file wrappercontents of which provisional application are herein incorporated byreference as though fully set forth at length.

FEDERAL RESEARCH STATEMENT

This invention described herein may be made, used, or licensed by or forthe United States Government for Government purposes without the paymentof any royalties thereon or therefore.

BACKGROUND OF INVENTION

1. Field of the Invention

The present invention relates to novel polyazido compounds of thegeneral formulae:

-   1. X═N₃; Y═CH₂N₃; A═B═N₃-   2. X═OH; Y═CH₂N₃; A═B═N₃-   3. X═ONO₂; Y═CH₂N₃; A═B═N₃-   4. X═NO₂ Y═CH₂N₃; A═B═N₃-   5. X═Y═NO₂; A═B═N₃-   12. X═Y═NO₂; A ═B═-   13. X═OH; A═B═-   6. Z═CH₂-   7. Z═O-   8. Z═NOH-   7—DNPH. Z═    including 2-azido-2-azidomethyl-1,3-diazidopropane (1),    2-azidomethyl-2-hydroxy-1,3-diazidopropane (2),    2-azidomethyl-2-nitrato-1,3-diazidopropane (3),    2-azidomethyl-2-nitro-1,3-diazidopropane (4),    2,2-dinitro-1,3-diazidopropane (5), methallyldiazide (6), a dimer of    methallyldiazide (6), comprising    3a,8a-Bis-azidomethyl-3a,4,8a,9-tetrahydro-3H,8H-bis[1,2,3]triazolo[1,5-a;1″,    5″-d]pyrazine (6-Dimer), 1,3-diazidoacetone (7), and    2-Oximido-1,3-diazidopropane (8).

Also shown are reaction intermediates of these compounds, including2,2-bis(chloromethyl)oxirane (9), and 2,2-bis(azidomethyl)oxirane (10).

In addition, a number of potentially useful energetic compounds havebeen prepared from the low molecular weight polyazido compounds above,includingN-2(azido-1-azidomethyl-ethylidene)-N″-(2,4-dinitrophenyl)-hydrazine(7-DNPH), 1,3-Bis(4-carboxytriazolyl)2,2-dinitropropane (12),Tris(4-carboxytriazolomethyl)methanol (13), Benzene-1,3,5-tricarboxylicacid tris(2-azido-1,1-bisazidomethyl-ethyl)ester (14), Adamantane1,3,5,7-tetracarboxylic acidtetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (15), Adamantanecarboxylic acid 2-azido-1,1-bisazidomethyl-ethyl)ester (16), cubane1,3,5,7-tetracarboxylic acid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (17), cubane 1,4-dicarboxylicacid bis(2-azido-1,1-bisazidomethyl-ethyl)ester (18).

In particular, the present invention relates to 2,2bis(azidomethyl)oxirane (10).

2. Description of Related Art

Low molecular weight compounds substituted with multiple energeticgroups exemplified by azide, nitrato and nitro groups are of interest asenergetic plasticizer ingredients, monopropellant formulations and asbuilding blocks for energetic polymers. Pentaerythritol tetranitrate,PETN, is widely used in blasting caps and detonation cords,bis(dinitropropyl)acetal/formal, BDNPA/F, azidomethylmethyloxetane(AMMO) and bis(azidomethyl)oxetane (BAMMO) are commonly used plasticizeringredients. Azido derivatives of pentaerythritol have been previouslydescribed (Frankel et al. U.S. Pat. No. 4,683,086). It was of interestto prepare compounds based on three- and four-carbon units with up tofour energetic groups thus producing compounds with a higher proportionof energetic groups per mole than the pentaerythritol derivatives. Thestructural unit of one of the compounds presented herein,2-azidomethyl-2-hydroxy-1,3-diazidopropane (compound 2, vide infra), hasbeen incorporated into energetic plasticizers formals and acetals(Rindone et al. U.S. Pat. No. 5,220,039) but the subject alcohol2-azidomethyl-2hydroxy-1,3-diazidopropane 2 has not previously beenprepared.

CAUTION: All organic azides described herein should be consideredextremely sensitive explosive compounds and should only be handled withproper safety precautions. 1,3-Diazidoacetone exploded subsequent topurification by distillation and extreme caution is urged in dealingwith all the azides.

These compounds are expected to be useful in novel explosive andpropellant applications as well as to serve as building blocks for thepreparation of novel energetic polymers capitalizing on the highreactivity of the azido groups. As a comparison PETN has four energeticgroups on a five-carbon framework whereas some of the compoundsdescribed herein have four energetic groups on a four- and athree-carbon unit. They are thus expected to provide much higher energyupon decomposition. The azido groups in these molecules can be convertedto triazole and tetrazole to prepare high nitrogen materials of interestin gas generating applications. The ability of azido groups to undergo1,3-dipolar cycloadditions, make these polyazido compounds usefulstarting materials for polymeric materials synthesis. In addition, thepolyazidopolyesters derived form polycarboxylic acids and the alcohol2-azidomethyl-2-hydroxy-1,3-diazidopropane 2, are of interest as coremolecules for the synthesis of dendrimers.

This invention relates to a series of novel compounds having the generalstructures A and B:

-   1. X═N₃; Y═CH₂N₃; A═B═N₃-   2. X═OH; Y═CH₂N₃; A═B═N₃-   3. X═ONO₂; Y═CH₂N₃; A═B═N₃-   4. X═NO₂ Y═CH₂N₃; A═B═N₃-   5. X═Y═NO₂; A═B═N₃-   12. X═Y═NO₂; A═B═-   13. X═OH; A═B═-   6. Z═CH₂-   7. Z═O-   8. Z═NOH-   7—DNPH. Z═    including 2-azido-2-azidomethyl-1,3-diazidopropane (1),    2-azidomethyl-2-hydroxy-1,3-diazidopropane (2),    2-azidomethyl-2-nitrato-1,3-diazidopropane (3),    2-azidomethyl-2-nitro-1,3-diazidopropane (4),    2,2-dinitro-1,3-diazidopropane (5), methallyldiazide (6), a dimer of    methallyldiazide (6), comprising    3a,8a-Bis-azidomethyl-3a,4,8a,9-tetrahydro-3H,8H-bis[1,2,3]triazolo[1,5-a;    1″, 5″-d]pyrazine (6-Dimer), 1,3-diazidoacetone (7), and    2-Oximido-1,3-diazidopropane (8).

Also shown are reaction intermediates of these compounds, including2,2-bis(chloromethyl)oxirane (9), and 2,2-bis(azidomethyl)oxirane (10).

In addition, a number of potentially useful energetic compounds havebeen prepared from the low molecular weight polyazido compounds above,includingN-2(azido-1-azidomethyl-ethylidene)-N″-(2,4-dinitrophenyl)-hydrazine(7-DNPH), 1,3-Bis(4-carboxytriazolyl)2,2-dinitropropane (12),Tris(4-carboxytriazolomethyl)methanol (13), Benzene1,3,5-tricarboxylicacid tris(2-azido-1,1-bisazidomethyl-ethyl)ester (14), Adamantane1,3,5,7-tetracarboxylic acidtetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (15), Adamantanecarboxylic acid 2-azido-1,1-bisazidomethyl-ethyl)ester (16), cubane1,3,5,7-tetracarboxylic acid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (17), cubane 1,4-dicarboxylicacid bis(2-azido-1,1-bisazidomethyl-ethyl)ester (18).

OBJECTS OF THE INVENTION

It is an object of the present invention to provide low molecular weightenergetic compounds with multiple energetic groups.

The other objects, features and advantages of the present invention willbecome more apparent in light of the following detailed description ofthe preferred embodiment thereof.

SUMMARY OF INVENTION

According to the present invention, there are provided low molecularweight polyazido compounds of the general formulae:

-   1. X═N₃; Y═CH₂N₃; A═B═N₃-   2. X═OH; Y═CH₂N₃; A═B═N₃-   3. X═ONO₂; Y═CH₂N₃; A═B═N₃-   4. X═NO₂ Y═CH₂N₃; A═B═N₃-   5. X═Y═NO₂; A═B═N₃-   12. X═Y═NO₂; A═B═-   13. X═OH; A═B═-   6. Z═CH₂-   7. Z═O-   8. Z═NOH-   7—DNPH. Z═    including 2-azido-2-azidomethyl-1,3-diazidopropane (1),    2-azidomethyl-2-hydroxy-1,3-diazidopropane (2),    2-azidomethyl-2-nitrato-1,3-diazidopropane (3),    2-azidomethyl-2-nitro-1,3-diazidopropane (4),    2,2-dinitro-1,3-diazidopropane (5), methallyldiazide (6), a dimer of    methallyldiazide (6), comprising    3a,8a-Bis-azidomethyl-3a,4,8a,9-tetrahydro-3H,8H-bis[1,2,3]triazolo[1,5-a;    1″, 5″-d]pyrazine (6-Dimer), 1,3-diazidoacetone (7), and    2-Oximido-1,3-diazidopropane (8).

Also shown are reaction intermediates of these compounds, including2,2-bis(chloromethyl)oxirane (9), and 2,2-bis(azidomethyl)oxirane (10).

In addition, a number of potentially useful energetic compounds havebeen prepared from the low molecular weight polyazido compounds above,includingN-2(azido-1-azidomethyl-ethylidene)-N″-(2,4-dinitrophenyl)-hydrazine(7-DNPH), 1,3-Bis(4-carboxytriazolyl)2,2-dinitropropane (12),Tris(4-carboxytriazolomethyl)methanol (13), Benzene1,3,5-tricarboxylicacid tris(2-azido-1,1-bisazidomethyl-ethyl)ester (14), Adamantane1,3,5,7-tetracarboxylic acidtetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (15), Adamantanecarboxylic acid 2-azido-1,1-bisazidomethyl-ethyl)ester (16), cubane1,3,5,7-tetracarboxylic acid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (17), cubane 1,4-dicarboxylicacid bis(2-azido-1,1-bisazidomethyl-ethyl)ester (18).

In particular, the present invention provides 2,2bis(azidomethyl)oxirane (10).

DETAILED DESCRIPTION

The preparation of the compounds claimed herein is detailed below.

The compounds2-azido-2-azidomethyl-1,3-diazidopropane1,2-azidomethyl-2-hydroxy-1,3-diazidopropane2, and2-azidomethyl-2-nitrato-1,3-diazidopropane 3 were prepared asshown in Scheme 1.

Commercially available methallyl dichloride was treated with sodiumazide in acetone under reflux for 16 hours to obtain methallyldiazide,6. Treatment of methallyldiazide 6 with sodium azide and manganese (III)acetate in acetic acid (J. Org. Chem. 1985, 50, 3647) afforded2-azido-2-azidomethyl-1,3-diazidopropane 1 as a clear colorless liquid.

The preparation of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 wasachieved by two different routes. In one method, methallyl diazide wasconverted to the corresponding epoxide, 2,2-bis(azidomethyl)oxirane 10,by treatment with mchloroperoxybenzoic acid (mcpba) in refluxingdichloroethane, which upon treatment with sodium azide provided2-azidomethyl-2-hydroxy-1,3-diazidopropane 2. In a second methodmethallyl dichloride was converted to 2,2-bis(chloromethyl)oxirane 9 asdescribed by Treves et al. (Chem. and Ind. 1971, 544). Treatment of2,2-bis(chloromethyl)oxirane 9 with sodium azide led to the formation of2-azidomethyl-2-hydroxy-1,3-diazidopropane 2.

2-Azidomethyl-2-hydroxy-1,3-diazidopropane 2 was converted to thecorresponding nitrate, 2-azidomethyl-2-nitrato-1,3-diazidopropane 3, bytreatment with nitronium tetrafluoroborate in the presence of collidine.

The preparation of 2-azidomethyl-2-nitro-1,3-diazidopropane 4, isdepicted in Scheme 2.

Commercially available tris(hydroxymethyl)nitromethane, (TRIS), wasconverted to the corresponding trimesylate, methanesulfonic acid3-methanesulfonyloxy-2-methanesulfonyloxymethyl-2-nitro-propyl ester 11according to a literature procedure (Wuest et al. Synthesis 1987, 742).Treatment of3-methanesulfonyloxy-2-methanesulfonyloxymethyl-2-nitro-propyl ester11with sodium azide in dimethylformamide at elevated temperature afforded2-azidomethyl-2-nitro-1,3-diazidopropane 4. The preparation of1,3-diazido-2,2-dinitropropane 5 is shown in Scheme 3.

Ozonation of methallyldiazide, 6, in methylene chloride provided1,3-diazidoacetone, 7, which was converted to its dinitrophenylhydrazonederivative, 7-DNPH. 1,3-diazidoacetone 7 was also prepared in one stepfrom 1,3-dichloroacetone by reaction with sodium azide. The structure of7-DNPH was established unequivocally by x-ray crystallographic analysis.

1,3-Diazidoacetone 7 was further converted to the corresponding oxime,2-oximido-1,3-diazidopropane 8, which was subjected to nitration toobtain 2,2-dinitro-1,3-diazidopropane, 5. A further tricyclic compound,3a,8a-bis-azidomethyl-3a,4,8a,9-tetrahydro-3H,8H-bis[1,2,3]triazolo[1,5-a;1″, 5″]pyrazine 6-DIMER was obtained from a slow dimerization ofmethallyl diazide at room temperature over several days.

The 1,3-dipolar cycloaddition reaction of organic azides with variousdienophiles with electron withdrawing groups is well established. Thepolyazides described herein can be treated with such dienophiles tosynthesize novel heterocyclic molecules.

To demonstrate the ease of such reactions, the polyazido compounds2,2-dinitro-1,3-diazidopropane 5 and2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 were treated withcommercially available propiolic acid under thermal conditions to obtainthe corresponding triazoles,1,3-bis(4-carboxytriazolyl)-2,2-dinitropropane 12 andtris(4-carboxytriazolomethyl)methanol 13 respectively (Scheme 4).

The diazido compounds prepared herein are expected to be importantintermediates in the preparation of energetic polymers due to their highreactivity with acetylenic and other unsaturated compounds. The facilereaction of the azido group with dipolarophiles as exemplified by thepreparation of the triazoles,1,3-bis(4-carboxytriazolyl)-2,2-dinitropropane 12 andtris(4-carboxytriazolomethyl)methanol13, can be exploited to providepolymeric materials by reaction with molecules containing multipleacetylenic functions or other unsaturated units as depicted in Scheme 5.

Another area of important utility of polyfunctionalized units is in thesynthesis of dendrimers. The triazdioalcohol2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 was treated with a varietyof poycarboxylic acid chlorides with rigid structures to obtain thecorresponding polyazidopolyesters shown below (Scheme 6).

Commercially available benzenitricarbonylchloride was treated with2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 in refluxing pyridine toobtain the corresponding triester benzene-1,3,5-tricarboxylic acidtris(2-azido-1,1-bisazidomethyl-ethyl)ester 14. The polyestersadamantine 1,3,5,7-tetracarboxylic acidtetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester 15, adamantinecarboxylic acid 2-azido-1,1-bisazidomethyl-ethyl)ester 16, cubane1,3,5,7-tetracarboxylic acid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester 17, and cubane 1,4-dicarboxylicacid bis(2-azido-1,1-bisazidomethyl-ethyl)ether 18 were prepared byfirst converting 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 to itssodium salt by reaction with sodium hydride and then adding the carbonylchlorides.

All new compounds prepared and claimed herein were characterized byspectral data and/or x-ray crystallography.

EXPERIMENTAL PROCEDURES Example 1 Preparation of Methallyldiazide, 6

To a solution of methallyl dichloride (10 g, 0.08 mol) in acetone (200mL) was added sodium azide (11.4 g, 0.175 mol) and the resultingsuspension was heated under reflux for 16 hours. The reaction mixturewas then cooled to room temperature and filtered to remove solids(sodium chloride and excess sodium azide), which were washed with oneportion of acetone (25 mL). The collected filtrate was concentratedunder reduced pressure to obtain methallyl diazide 6. ¹H NMR (CDCl₃):δ3.85 (s, 4H), 5.29 (s, 2H).

Example 2 Preparation of 1,3-Diazidoacetone, 7

Methallyldiazide 6(2.5 g) was dissolved in methanol (100 mL) in a roundbottom flask and cooled to 78° C. Ozone was bubbled into the solutionfor 1.5 hrs till blue color persisted. Dimethyl sulfide (2 mL) was addedto the reaction mixture at 78° C. and then the mixture was allowed towarm up to room temperature and stirred at room temperature for 30minutes. The reaction mixture was then concentrated in vacuo to obtain1,3-diazidoacetone, 7. ¹H NMR (CDCl ₃)δ4.07 (s)

Example 3 Preparation DNPH derivative of 1,3-Diazidoacetone 7

N-2(azido-1-azidomethyl-ethylidene)-N″-(2,4-dinitrophenyl)-hydrazine(7-DNPH): To a suspension of 0.25 g of 2,4-dinitrophenylhydrazine in 5ml of methanol and was added add 0.5 ml of concentrated sulphuric acidcautiously. The warm solution was filtered and added to a solution of1,3-diazidoacetone (150 mg) in 2 ml of methanol. SolidN-2(azido-1-azidomethyl-ethylidene)-N″-(2,4-dinitrophenyl)-hydrazine7-DNPH formed and was collected by filtration and recrystallized fromethanol. ¹H NMR (CDCl ₃) δ 9.16 (s, 1H), 8.39 (d, 2H), 7.98 (d, 2H),4.33 (s, 2H), 4.15 (s, 2H)¹³C NMR (CDCl₃) δ145.807, 144.568, 139.227,130.620, 130.198, 123.197, 116.532, 54.791, 47.764.

Example 4 Preparation of 1,3-Bis(4-carboxytriazolyl)-2,2-dinitropropane12

Dissolved 2,2-dinitro-1,3-diazidopropane 5 in CDCl₃ in an nmr tube.Added a few drops of propiolic acid (excess). Heated the tube at 60° C.for 3 hrs. Decanted out the solution. The residue was dissolved in DMSO.Water was added to the DMSO solution. The product,1,3-bis(4-carboxytriazolyl)-2,2-dinitropropane 12, was precipitated outand was collected by filtration. ¹H NMR (DMSO-d₆) δ8.70 (s, 2H), 5.98(s, 4H) ¹³C NMR (DMSO-d₆) δ162.045, 140.792, 132.454, 116.124, 50.668.

Example 5 Preparation of 2-Oximido-1,3-diazidopropane, 8

To a solution of 1,3-diazidoacetone (2.5 g from the above reaction) inethanol (150 mL), was added hydroxylamine hydrochloride (1.48 g) andsodium acetate (5.83 g). The reaction mixture was stirred at roomtemperature for 48 hours. Water was then added and the reaction mixturewas extracted with ether. The combined organic layer was washed withwater and saturated sodium bicarbonate solution. The organic layer wasthen dried over sodium sulfate and concentrated under reduced pressure.The resulting residue was chromatographed on silica gel to obtain2-oximido-1,3-diazidopropane 8. ¹H NMR (CDCl₃) δ4.27 (s, 2H), 3.99 (s,2H), 8.99 (s, 1H); ¹³C NMR (CDCl₃) δ151.94, 51.06, 45.31

Example 6 Preparation of 2,2-Dinitro-1,3-diazidopropane, 5

To a refluxing solution of 2-oximido-1,3-diazidopropane (1.2 g) inmethylene chloride (30 mL) was added dropwise, a solution ofconcentrated nitric acid (6 mL) in methylene chloride (10 ml) to whichcatalytic amounts of urea and ammonium nitrate were added. The reactionmixture was heated under reflux for an additional 2 hrs till the bluegreen color was gone. The reaction mixture was then cooled to roomtemperature, diluted with water and the resulting solution was extractedwith ethyl acetate. The organic layer was dried over sodium sulfate andconcentrated under reduced pressure. The resulting residue waschromatographed to obtain 2,2-dinitro-1,3-diazidopropane 5. ¹H NMR(CD₃COCD₃): δ4.7 (s); ¹³C NMR (CD₃COCD₃): δ50.73, 115.14

Example 7 Preparation of Methallyldiazide dimer, (6-DIMER)

Methallyl diazide 6 on standing under ambient conditions for 4–6 weeksdeposited crystals which were filtered and washed with hexane andrecrystallized from ethanol to obtain 6-DIMER). ¹H NMR (CDCl ₃): δ 3.29(AB, J_(AB)=14.9 Hz, 2H), 4.10, (AB, J_(AB)=14.9 Hz, 2H); 3.54 (AB,J_(AB)=12.8 Hz, 2H, 3.60 (AB, J_(AB)=12.8 Hz, 2H); 4.02 (AB, J_(AB)=16.6Hz, 2H), 4.22 (AB, J_(AB)=16.6 Hz, 2H); ¹³C NMR (CDCl ₃): δ 43.99,50.95, 61.00, 72.83

Example 8 2-Azido-2-azidomethyl-1,3-diazidopropane 1

A suspension of methallyl diazide 6(0.35 gm, 2.5 mmol), sodium azide(2.5 gm, 38.5 mmol), and manganese (III) acetate in acetic acid (10 mL)was heated at 85° C. for 20 minutes and then at 105° C. for 30 minutes.The resulting pale yellow homogeneous solution was cooled to roomtemperature and poured into water (100 mL). The mixture was thenextracted with methylene chloride (3×25 mL). The organic extracts werecombined, dried over sodium sulfate and concentrated, and the residuewas purified chromatographically to obtain2-azido-2-azidomethyl-1,3-diazidopropane 1, as a clear colorless oil. ¹HNMR (CDCl₃): δ3.51 (s); ¹³C NMR (CDCl₃): 52.91, 64.92.

Example 9 2,2-Bis(azidomethyl)oxirane, 10

A suspension of methallyl diazide (5.5 gm, 0.04 mol) and mcpba (9.5 gm,77% max) in 1,2-dichlorethane was heated under reflux for 14 hours. Thereaction mixture was cooled to room temperature and filtered. Thefiltrate was washed with saturated sodium bicarbonate solution (2×100mL). The organic layer was dried over sodium sulfate and concentratedunder reduced pressure to provide a residual oil with some solids. Theresidue was dissolved in ether and the ethereal solution was washed withsaturated sodium bicarbonate solution (2×100 mL), dried over sodiumsulfate and concentrated under reduced pressure to obtain2,2-Bis(azidomethyl)oxirane, 10. ¹H NMR (CDCl ₃): δ2.88 (s, 1H), ABquartet centered at 3.50 (4H, 13.3 Hz), 2.90 (s, 2H).

Example 10 2-Azidomethyl-2-hydroxy-1,3-diazidopropane 2 A. From2,2-Bis(azidomethyl)oxirane, 10

To a solution of methallyldiazide 6 (0.5 gm, 3.25 mmol) in acetone (20mL) and water (5 mL) was added sodium azide (0.34 gm, 5.23 mmol) and theresulting mixture was heated under reflux for 3 hours. The reactionmixture was concentrated under reduced pressure and the residue waspartitioned between methylene chloride and waster. The organic layer wasseparated, dried over sodium sulfate and concentrated under reducedpressure. The residue was chromatographed on silica gel to obtain pure2-azidomethyl-2-hydroxy-1,3-diazidopropane 2. ¹H NMR (CDCl₃): δ2.80 (s,br, 1H), 3.40 (s, 6H); ¹³C NMR (CDCl₃): δ54.53, 74.40.

B. From 2,2-Bis(chloromethyl)oxirane, 9:

To a solution of 1,3-diazidoacetone 7(10 gms, 0.07 mol) in aq. acetone(20 mL water, 150 mL acetone) was added sodium azide (15 gm, 0.23 mol)and the resulting mixture was heated under reflux for 14 hours. Thereaction mixture was concentrated under reduced pressure and partitionedbetween water and methylene chloride. The organic layer was separated,dried over sodium sulfate and concentrated to obtain a residue that waschromatographed to obtain pure2-azidomethyl-2-hydroxy-1,3-diazidopropane 2.

Example 11 Tris(4-carboxytriazolomethyl)methanol, 13

To a solution of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 (0.19 gm),in chloroform was added propiolic acid (0.22 gms) and the solution washeated at reflux for 14 hours. The precipitated product was filtered,and recrystallized from water to obtain puretris(4-carboxytriazolomethyl)methanol 13. ¹H NMR (DMSO-d6): δ4.57 (s,6H), 6.10 (s, 1H), 8.55 (s, 3H).

Example 12 2-Azidomethyl-2-nitrato-1,3-diazidopropane 3

To a cooled (0° C.) solution of nitronium tetrafluoroborate (130 mg,1.12 mmol) in acetonitrile (2 mL) under nitrogen atmosphere a solutionof collidine (127 mg, 1.04 mmol) in acetonitrile (1 mL) was addeddrop-wise via syringe. The resulting mixture was stirred at 0° C. for 45min. 2-Azidomethyl-2-hydroxy-1,3-diazido propane, 2, (100 mg, 0.5 mmol)in acetonitrile (2 mL) was added drop-wise and the resulting mixture wasstirred at room temperature for 48 hours. The reaction mixture waspoured over water (25 mL) and extracted with ethyl acetate (2×15 mL).The combined organic layer was washed with water (1×25 mL), brine (1×25mL) and dried (Na ₂SO ₄). Evaporation of the solvent and chromatographicpurification of the residue afforded the2-azidomethyl-2-nitrato-1,3-diazidopropane 3 as a colorless liquid. ¹HNMR (CDCl₃): δ3.78 (s, 6H); ¹³C NMR (CDCl₃): 50.31, 89.07.

Example 13 2-Azidomethyl-2-nitro-1,3-diazidopropane 4

To a solution of the trimesylate, methanesulfonic acid3-methanesulfonyloxy-2-methanesulfonyloxymethyl-2-nitro-propyl ester 11(1 gm, 2.6 mmol) in dimethylformamide (10 mL) was added sodium azide(0.6 gm, 9.2 mmol) and the resulting mixture was heated under reflux for14 hours. The reaction mixture was then cooled to room temperature,diluted with water (50 mL) and extracted with ethyl acetate (50 mL). Theorganic extract was washed with water, dried over sodium sulfate andconcentrated under reduced pressure to give a residue that waschromatographed to obtain pure 2-azidomethyl-2-nitro-1,3-diazidopropane4. ¹H NMR (CD₃COCD₃): δ4.01 (s); ¹³C NMR (CD₃COCD₃): 60.36, 95.30.

Example 14 Reaction of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 withbenzene tricarbonyl chloride Benzene-1,3,5-tricarboxylic acidtris(2-azido-1,1-bisazidomethyl-ethyl)ester 14

To a solution of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 (0.4 gm)in dry pyridine (10 mL) was added benzene tricarbonyl chloride (0.18 gm)and the resulting mixture was heated at reflux overnight. The mixturewas then allowed to cool to room temperature and concentrated underreduced pressure. The residue was triturated with ethyl acetate andfiltered. The filtrate was concentrated and the residue waschromatographed on silica gel to obtain pure triesterbenzene-1,3,5-tricarboxylic acidtris(2-azido-1,1-bisazidomethyl-ethyl)ester 14. ¹H NMR (CDCl₃): δ3.91(s, 6H), 8.8 (s, 1H); ¹³C NMR (CDCl₃): 51.25, 84.08, 130.98, 135.52,163.53.

Example 15 Reaction of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 withcubane dicarbonyl chloride Cubane 1,4-dicarboxylic acidbis(2-azido-1,1-bisazidomethyl-ethyl)ester 18

To a solution of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2(0.5 gm) ina dry THF (25 ml) was added sodium hydride (125 mg) and the resultingmixture was heated at reflux overnight. The reaction mixture was cooledand cubane dicarbonyl chloride (325 mg.) in THF was added at roomtemperature and the reaction mixture was heated at reflux for another 24hrs. The mixture was then allowed to cool and THF was removed from underreduced pressure and ethyl acetate solvent was added. The resultingsolution was washed with dilute HCl and saturated sodium chloridesolution. The resulting ethyl acetate solution was evaporated and theproduct was purified with column chromatography to obtain cubane1,4-dicarboxylic acid bis(2-azido-1,1-bisazidomethyl-ethyl)ester 18. ¹HNMR (CDCl ₃): δ3.74 (s, 12H), 4.29 (s, 6H);

Example 16 Reaction of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 withcubane tetracarbonyl chloride Cubane 1,3,5,7-tetracarboxylic acidtetrakis (2-azido-1,1-bisazidomethyl-ethyl)ester 17

To a solution of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2(0.5 gm) ina dry THF (25 ml) was added sodium hydride (125 mg) and the resultingmixture was heated at reflux overnight. The reaction mixture was cooledand cubane tetracarbonyl chloride (220 mg.) in THF was added at roomtemperature and the reaction mixture was heated at reflux for another 48hrs. The mixture was then allowed to cool and THF was removed from underreduced pressure and ethyl acetate solvent was added. The resultingsolution was washed with dilute HCl and saturated sodium chloridesolution. The resulting ethyl acetate solution was evaporated and theproduct was purified with column chromatography to obtain cubane1,3,5,7-tetracarboxylic acid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester17. ¹H NMR (CDCl₃): δ3.75 (s,24H), 4.79 (s, 4H)

Example 17 Reaction of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 withAdamantane tetracarbonyl chloride adamantane 1,3,5,7-tetracarboxylicacid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester 15

To a solution of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2(0.5 gm) ina dry THF (25 ml) was added sodium hydride (125 mg) and the resultingmixture was heated at reflux overnight. The reaction mixture was cooledand adamantane tetracarbonyl chloride (240 mg.) in THF was added at roomtemperature and the reaction mixture was heated at reflux for another 48hrs. The mixture was then allowed to cool and THF was removed from underreduced pressure and ethyl acetate solvent was added. The resultingsolution was washed with dilute HCl and saturated sodium chloridesolution. The resulting ethyl acetate solution was evaporated and theproduct was purified with column chromatography to obtain adamantane1,3,5,7-tetracarboxylic acidtetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester15. ¹H NMR (CDCl ₃): δ3.8(s), 2.28 (s)

Example 18 Reaction of 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2 withAdamantane carbonyl chloride: Adamantane carboxylic acid2-azido-1,1-bisazidomethyl-ethyl)ester 16

To a solution of 2-azidomethyl-2hydroxy-1,3-diazidopropane 2(0.5 gm) ina dry THF (25 ml) was added sodium hydride (125 mg) and the resultingmixture was heated at reflux overnight. The reaction mixture was cooledand adamantane carbonyl chloride (990 mg.) in THF was added at roomtemperature and the reaction mixture was heated at reflux for another 24hrs. The mixture was then allowed to cool and THF was removed from underreduced pressure and ethyl acetate solvent was added. The resultingsolution was washed with dilute HCl and saturated sodium chloridesolution. The resulting ethyl acetate solution was evaporated and theproduct was purified with column chromatography to obtain adamantanecarboxylic acid 2-azido-1,1-bisazidomethyl-ethyl)ester 16.

¹H NMR (CDCl3): δ3.72 (s), 1.97 (s), 1.9 (s), 2.01 (s)

Other features, advantages, and specific embodiments of this inventionwill become readily apparent to those exercising ordinary skill in theart after reading the foregoing disclosures. These specific embodimentsare within the scope of the claimed subject matter unless otherwiseexpressly indicated to the contrary. Moreover, while specificembodiments of this invention have been described in considerabledetail, variations and modifications of these embodiments can beeffected without departing from the spirit and scope of this inventionas disclosed and claimed.

1. 2,2 Bis(azidomethyl)oxirane.